JPS5984897A - Eta5-methoxycarbonylcyclopentadienyl cobalt complex - Google Patents

Abstract

NEW MATERIAL:The compound of formula I -III [R1 is 4-12C unsubstituted polyene residue having 2-4 double bonds, or a polyene group (substituted with 1-4C alkyl, phenyl or cyanomethylene); Co is coordinated to the diene part of the polyene; R2 is (1-4C alkyl or phenyl-substituted) metallocyclic cylopentadiene residue]. EXAMPLE:eta<4>-Norbornadiene-eta<5>-methoxycarbonylcyclopentadienyl cobalt. USE:A catalyst for the preparation of a pyridine derivative. It can by obtained economically in an industrial scale. PROCESS:The objective compound can be prepared by reacting methoxycarbonylcyclopentadienyl sodium with tristriphenylphosphine cobalt monohalogenide in a solvent at 0-80 deg.C for 0.1-24hr, adding a polyene (e.g. butadiene) or acetylene compound corresponding to the objective compound to the system, and reacting at 0-150 deg.C for 0.5-24hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing cobalt complexes by applying a new method of preparation. The complex obtained here is a new substance having the structure of meI.oxyluponylcyclopentadienylcobaltoboriene. Furthermore, the present invention relates to an improved production method for producing a pyridine derivative from an alkyne and a nitrile using the complex obtained here as a catalyst.

A method for producing a substituted pyridine from an alkyne and 2I-lyl using a cyclopentadienyl cobalt cyclic diene complex and the same as a catalyst is already known. For example, using a cycloalkaline dienylcobal I/cycloalkadiene complex and this as a catalyst, two molecules of alkyne and one nitrile
It is known that molecules undergo bond cyclization at their respective double bonds to obtain substituted pyridines (Japanese Unexamined Patent Publication No. 135-1989).
084, JP 52-25780, U.S. Patent No. 4267
No. 329). However, it has been extremely difficult to synthesize substituted cyclopentadienylcobaltboriene complex compounds in which an electron-withdrawing group is bonded to cyclopentadiene.

The present invention solves this difficulty by a novel preparation method, and η5
The present invention discloses a method for obtaining a -methoxycarbonylcyclopentadienyl cobalt polyene complex in good yield. The η5-methoxycarbonylcyclopentadienyl cobalt polyene obtained here was synthesized for the first time by the method of the present invention.

The η5-methoxylponylcyclopentadienyl cobal) polyene complex compound according to the present invention is prepared by the following route.

[In formula (IV), X is halogen, and in formula (V), R
1 is an unsubstituted polyene with 4 to 12 carbon atoms and 2 to 4 double bonds or a substituted polyene with 1 to -4 substituents (the substituent is an alkyl group with 1 to 4 carbon atoms, phenyl or cyanomethylene group). However, R1 excludes polyenes consisting only of aromatic rings. ] Alternatively, instead of formula (V), formula (Vl) or formula (■
) [In the formulas (Vl) and (■), R'2 is substituted or unsubstituted acetylene (the substituent is an alkyl group having 1 to 4 carbon atoms or a phenyl group, the number of substituents is 1 to 2), On the other hand, R
2 is an organic residue of meclocyclic cyclopentadiene composed of an R22 molecule and a cobalt atom, and the substituents are similar to R2. ] (■) The starting material methoxycarbonylcyclopentagenyl sodium is Raus
The method by ch et al. [J, Am. Chem. Soc.

102, 1196 (1980)]. Among the tristriphenylphosphine copartomonohalogenides, for example, tristriphenylphosphine cobalt monochloride can be easily obtained by reacting cobalt chloride and I.liphenylphosphine in the presence of a reducing agent. [Inorg. Chim. A
cta, 3, 227 (1969)].

The reaction of formula (IV) involves reacting approximately equivalent molar or 4-1,000 molar excess of MeI-xycarbonylcyclopentadienyl sodium in a solvent at a temperature of 0.60 to 80°d for 0.1 to 24 hours. This can be done by The reaction product obtained here can be isolated and purified, but it can also be used as it is for the next reaction. (V, Vl
In the reaction of formula (IV), polyenes or acetylenes corresponding to the target substance are added to the reaction solution of formula (IV), and the reaction is heated from 0°C to 1°C.
This can be carried out by reacting at 50°C for 0.5 to 24 hours.

The polyenes used here can be selected from a wide range of
For example, butadiene, isoprene, substituted or unsubstituted cyclopentadiene, dicyclopentadiene, hexadiene, norbornadiene, intene, cyclooctadiene,
Examples include cyclooctatetraene, azulene, cyclododecatriene, alkyl or phenyl substituted products thereof, and cyanomethylene substituted products. However, it does not react with polyenes that only have aromatic rings, such as benzene, toluene, and xylene. In addition, as acetylenes,
Acetylene, methylacetylene.

Etheracetylene, phenylacetylene, diphenylacetylene, etc. can be mentioned.

All reactions are preferably carried out in an inert atmosphere free of moisture, oxygen, carbon gas, etc. After the reaction product liquid is concentrated, it can be separated and purified by applying column chromatography.

18) The leaked η5-methoxyluponylcyclopentadienylcobal I/polyene complex is relatively stable in air.

The characteristics of the present invention are that methoxylponylcyclopentagenylna].lium is selected as a starting material, and this is reacted with tristriphenylphosphine cobal I monohalogenide. The point is to react the corresponding polyene or acetylene. Regarding the reaction of formula (II/), examples using sodium cyclopentadienyl as a starting material are known, and the present invention is the first example using sodium methoxycarbonylcyclopentagenyl as a starting material. The reaction of reaction products with polyenes or acetylene is also completely unknown.

Conventionally, cyclopentadienyl cobalt foliene complexes were generally synthesized by reacting dicarbonyl-η5-cyclopentadienyl cobalt with polyene or acetylene [Shin Jikken Kagaku Koza Vol. 12, pp. 189-190 ( round neck)]. However, it was difficult to synthesize the η5-methoxyluponylcyclopentadienylcobaltboriene 31N compound of the present application using such known methods. As a result of diligent efforts, the inventor of the tree discovered a new synthesis method and was able to complete the present application.

The product obtained by formula (V) is a complex bonded to a cobalt atom in the form of methoxycarbonylcyclopentadienyl η5, and furthermore, the polyene defined by R has a coordinate bond with the cobalt atom at the diene moiety. It has a similar structure. That is, this complex has the formula (i) CH600C@l-co=R1(I) [In formula (1), R1 is an unsubstituted polyene having 4 to 12 carbon atoms having 2 to 4 double bonds or 1 to A substituted polyene having 4 substituents, in which the cobalt atom is a coordinate bond with the diene moiety in the polyene (the substituent is an alkyl group having 21 to 4 carbon atoms, a phenyl group, or a cyano group). methylene group). However, R excludes polyenes consisting only of aromatic rings. ].

In formula (Vl), instead of R1, two molecules of acetylene or its derivative (R'2) react, and the product is a mecrocyclic cyclopentadiene ring formed by the triple bond of the acetylene and cobalt. , and is a substance in which triphenylphosphine is coordinately bonded with cobalt. That is, the structure of this complex is the formula (I) [In formula (11), R2 is a substituted or unsubstituted meclocyclic cyclopentadiene residue (the substituent has 1 to 4 carbon atoms)
alkyl group or phenyl group, the number of substituents is 1 to 4
). ].

On the other hand, in formula (■), instead of the reaction product I·liphenylphosphine of formula (Vl), η5-methoxycarbonylcyclopentagenyl cobaltopal I·-cobal I
It has a structure in which the compound forms a bond and is bonded, and furthermore, the diene is coordinated to the copalccyclopentadienyl ring. That is, the structure of this complex is represented by formula (III) [In formula (Ill), R2 is the same as R2 in formula (II). ].

All of these substances are new substances, and their structures have been determined using elemental analysis, infrared absorption, NMRl, etc.

The η5-methoxyluponylcyclopentadiene cobalt polyene complex shown in the present invention exhibits extremely high activity when used as a catalyst in a reaction that produces substituted or unsubstituted pyridine from alkynes and 2I-lyls. It was found that it has. Cycloalkagenyl cobalt complexes generally have catalytic activity in the synthesis of pyridine derivatives through the cocyclization reaction of alkyne and nitrile, but substituted cyclopentadienyl cobalt complexes in which cyclopentadiene is substituted with an electron-withdrawing group have even higher activity. It is.

In particular, the η5-methoxyluponylcyclopentadienyl cobaltboriene complex disclosed in the present invention exhibits extremely excellent catalytic performance.

The used part of the catalyst exhibits its effectiveness at a concentration of O, 1 mmof/liter or more in the reaction system. And it is usually not necessary to make it more than lOOm mol/liter.

Regarding the reaction raw materials, the use of the catalyst shown in "-" can be applied to a wide range of alkynes and nitriles as in the prior art.

Alkynes include terminal alkynes, dialkyl, diallyl, such as acetylene, alkyl, alke;, lu and allyl acetylene.

Alkylalkenyl-acetylene and alkylaryl-
Disubstituted acetylenes such as acetylene, these alkynes may be mixtures of different alkynes.

On the other hand, as the nitrile, heptanitriles such as alkyl-, allyl-, and alkenyl-nitriles, and polyfunctional nitriles in which a plurality of these trile groups are present can be suitably used.

The molar ratio of alkyne to nitrile can be appropriately selected within the range of 0.01 to 100. However, in order to reduce the amount of by-products, it is better to have diI-lyl present in excess rather than alkyne.

The method of the present invention involves adding a catalyst and optionally a solvent to an excess of nitrile in the presence or absence of a solvent, and proceeding with the reaction by adding the alkyne at a temperature of 50 to 200'O. I can do it. As the solvent, saturated hydrocarbons, aromatic hydrocarbons, ethers, esters, alkylcarboxamides, etc. can be widely used, although their use is not essential. Furthermore, it is of course possible to use the complex compound obtained in the present invention immediately for the synthesis of substituted pyridine without purifying it for 1 minute. This method is an advantageous choice for use as a catalyst in the industry.

The method of the present invention is characterized by strong catalytic activity and high reaction rate.

Another major feature is that the amount of aromatic hydrocarbons produced as a by-product along with the production of substituted pyridine can be significantly reduced.

As a result, industrially satisfactory productivity and product concentration can be easily obtained.

In particular, when a lower alkyne such as acetylene is used as the By material, the reaction can proceed at a sufficiently practical rate at a much lower pressure than in known systems. This fact is extremely important from a practical standpoint, considering that lower alkynes have an extremely high risk of decomposition and explosion due to pressurization.

It can be said that, for the first time, the present invention has made it possible to industrially easily produce, for example, industrially important products such as vinylpyridine, α-picoline, pyridine, etc. from acetylene and nitrile.

The embodiments of the present invention will be described below with reference to Examples, but the scope of the present invention is not limited by these embodiments.

Example 1 Preparation of η4-norbornadiene-η5-methoxyluponylcyclopencdienyl cobalt.

Dimethyl carbonate (1,5n+l) was added to a tetrahydrofuran solution of cyclopentadienyl sodium (7ml of 2mmol/ml solution), and 1.5n+l was added under nitrogen atmosphere.
Heat to reflux for an hour. (47) The reaction solution was mixed with tristriphenylphosphine cobalt monochloride (8,81
g, 10 mmol) in benzene (20 ml). The mixture immediately becomes a red liquid, but after stirring occasionally to complete the reaction, norbornadiene (3 ml) is added and the mixture is heated under reflux on a hot water bath for 1 hour. After cooling, pass through a short alumina column to remove insoluble matter, and collect the red-orange liquid eluted with benzene. The solvent was distilled off under reduced pressure and heating, hexane (20 ml) was added to the residue, and the mixture was stirred overnight. The precipitated triphenylphosphine (4.64 g) was poured into decane and filtered, and the red liquid was poured onto alumina chroma I again. Further triphenylphosphine (2.06 g) is recovered from the colorless liquid flowing out with hexane.

The solvent was distilled off under reduced pressure from the red-orange liquid flowing out with benzene/hexane (1:1), and the residue was heated and dissolved in hexane and left in the refrigerator to give orange crystals (2.0 g; yield 73%).
) is obtained. Melting point 50-51°C. Analysis value C61,27
%, H5, 52%. 8 as C14H1502Co
1 calculation value C61°32%, H5,51%. I R (Nuj
ol): l 720.

1700cf'(C=C),'H-NMR (CD
2 C12): 60.77.2.91, 3.14
(C7HLI); 3.81 (CH3);
4.88, 4.91ppm (C5H/l)
.

Example 2 Preparation of η'-1,5-cyclooctadiene-η5-methoxycarbonylcyclopentadienyl cobalt.

In the same manner as in Example 1, cyclopencgenyl sodium (7 mmol) and tristriphenylphosphine cobalt monochloride triphenylphosphine-nylcyclopentadienyl cobalt were mixed and 1,5-cyclooctadiene (2 ml) was added. Leave at room temperature for 111 minutes. The procedure was carried out in the same manner as in Example 1 to obtain reddish brown crystals (0.45 g; yield 38%). Melting point 86-87°00 Analysis value C62.13%, H6,
59%. Calculated value C6 as C+sHu02 Co
2.07%, H6.60%. I.R. (Nujof):
1720, 1700c++T' (C=0), "H-
NMR (CDC 13 ): δ 1.
'63, 2.38.

3,58 (C8H12); 3.95 (CH3
); 4, 40, 5.03ppm (C5H4)
.

Example 3 η4-cyclooctatetraene-η5-methoxycarbonylcyclopentadienyl cobalt.

According to Example 1, bistriphenylphosphine-η5
-Methoxycarbonylcyclopentadienyl cobalt solution (5 mmol) is prepared, cycloophtate I.Laene (1 ml) is added thereto, and the mixture is refluxed in a nitrogen atmosphere for 1 hour. The solvent was distilled off, dissolved in hexane, and subjected to alumina chromatography. Triphenylphosphine (2.8 g) is recovered from the colorless liquid flowing out with benzene/hexane (1:1). The reddish-brown liquid eluted with benzene/hexane (2:1) is concentrated, hexane is added, and the mixture is allowed to stand to give reddish-brown crystals (0.46 g, yield 32%). Melting point 6
7-68℃. Analysis value C62.84%, H5.

25%, Cps calculated as H+s 0 2 Co C62, 95%, H5, 28%. I R (Nuj
ol): l 720, 1700 (C=0);
1630c+n” (C=C).1H-NMR
(CD2 C 12): δ3.

64, 5.56 (C8 H8); 3.90 (
CH3); 4.55, 5.1ippm (C5H
4).

Example 4 Production of η4-butadiene-η5-methoxycarbonylcyclopentadienyl cobalt.

The bistriphenylphosphine-η5-methoxycarbonylcyclopentadienyl cobalt prepared according to Example 1 is placed in a 100 ml flask, the upper space of which is replaced with butadiene, the mixture is tightly capped, and the mixture is shaken. After standing overnight at room temperature, the solvent was distilled off and applied to Alumina Chroma I. Triphenylphosphine (t
．． 5g) is recovered.

When the red liquid obtained by elution with benzene/hexane (1:l) was dried under reduced pressure and left to stand, the remaining 111''?
A red oil crystallizes (0.25 g, 42% yield). Melting point 4 0-4. 2°C (in nitrogen-filled capillary)
, I R (Nujol): 1 7 1 0 cm-
' (C=0), "HNMR (CD2 C12)
: δ −0,28°1.84,5.11 (C
4H6), 3.74 (CH3); 4.98
, 5.29 ppm (C5H4).

Example 5 Preparation of I.liphenylphosphine-η5-methoxycarbonylcyclopentadienyl(tetraphenylcopal')cyclopentadiene).

Bistriphenylphosphine-η5- according to Example 1
A methoxycarbonylcyclopentadienyl cobalt solution (5 mmol) was prepared, and diphenol acetylene (1,7
8 g, 10 mmol) and incubate for 11 minutes. After concentration, alumina chromatography was performed and benzene/hexane (2:
The reddish-brown solution flowing out in step 1) was concentrated and hexane was added to obtain dark brown crystals (1.6 g, yield 40%). Melting point 153-155°C. Analysis value C77,84,H5,
12%, At 39 as C55H42Q 2 P Co: values C79°49%, H5,29%. I.R.
(Nujol): 1720cm"(C=O),'
H-NMR (CDC13): δ3.82 (CH3);
4.69, 5.43 (C5H4); 6.4-7.
4ppm (C6H5).

Example 6 [η5-methoxycarbonylcyclopentadienyl(cobaltacyclopentadiene)co-η5-methoxycarbonylcyclopentadienyl(Co-Co
)Manufacturing of.

According to Example 1, bistriphenylphosphine-η5
-Methoxycarbonylcyclopentadienyl Cobalt solution (4 mmol) was prepared and put into a 200 ml flask, and the upper space was replaced with acetylene. Seal tightly and mix with FIJJ for 10 minutes. After concentration, it is applied to alumina chromatography.

After thoroughly washing the column with benzene/hexane (1:1), the dark brown liquid eluted with benzene was concentrated, hexane was added, and the mixture was evaporated to give black crystals (0.24 g).

Furthermore, the green liquid flowing out was dried with benzene, hexane was added, and the mixture was left in the refrigerator to produce green crystals (0°05g, yield 3).
%) to 1. Melting point 68-70°0 (in g-substance packed capillary) Analysis value C51, 94%, H4, 34%, C
+a H+a Oa Co 2 as A1 Arithmetic +6
C51, 95%, H4, 36%. I R(Nu
jof): 1710, 1695cm'' (C=0
), 'H-NMR (CDCl3): δ3
．． 85, 3.90 (CH3); 4.92, 5.
10,5.52,5°58 (C5H4);4.
99.8.25 ppm (C, +H4').

Example 7 Under an argon atmosphere, 76 mt (0, 26 mmol) of η4-norbornadiene-η5-methoxycarbonylcyclopentagenyl cobalt prepared by the method of Example 2 was added to 60 mmol of toluene in a 100 ml stainless steel autoclave.
Dissolve and prepare with ml, and add 20g of acrylonitrile.
I prepared it. OI crepe is replaced with acetylene,
After heating from normal pressure to 150° C., acetylene was constantly supplied at 1 3 kg/cm 2G. 6
2-vinylpyridine was synthesized by reacting for 0 minutes, and the reaction solution was analyzed by gas chromatography.

In addition, the acetylene supply pressure was set to 1 3 kg/cm 2G.
The reaction was carried out in exactly the same manner as described in Section 2, except that the reaction was changed from 5 kg/cm 2Q to 5 kg/cm 2Q. The results of these reactions are shown in Table 1.

Example 8 As a catalyst, triphenylphosphine-η5-methoxycarbonylcyclopentadiene (tetraphenylcobaltacyclopencdiene (catalyst II) 53 mg (0,07 mmol) prepared by the method of Example 5, acrylonitrile 5, 80 ml of Og and toluene-1 formula
The reaction was carried out in exactly the same manner as in Example 7 except that the reaction was changed to .

The reaction pressure was 13 kg/Cm 2G. The reaction results are shown in Table 1.

Example 9 3 mg of η4-norbornadiene-η5-methoxycarbonylcyclopentadienylcopal (61111) prepared by the method of Example 1 as a catalyst.

(0,23m mol), acrylonitrile 17
．． The reaction was carried out in the same manner as in Example 7 except that 8 g and toluene were changed to 54 ml. Reaction pressure is 13kg/cI
It was 112G. The reaction results are shown in Table 1.

Example 10 [η5-methoxypowerponylcyclobentadienyl(cobaltacyclopentadiene)Coli 5-methoxypowerponylcyclopestadienylcobajlz)(CO-CO)(CO-CO)( Catalyst ■) 33
mg (0.08 mmol).

A reaction was carried out in the same manner as in Example 7 using 6 g of acrylonitrile and 18 ml of toluene. The reaction results are shown in Table 1.

Comparative Examples 1-3 The same operations as in Example 7 were repeated using known catalysts. As a specific example, bis dichloropentadienyl cobalt diene-η5-cyclopentadiene cobalt (Mr.
) and η'-1-exo-cyanomethylcyclopentadiene-ηS-cyclopentadienyl cobalt (catalyst ■
) and catalyst (1) in equimolar amounts.

26 mmol was added. Acrylonitrile 5.0
g. 80 ml of toluene was charged as a solvent. Acetylene was supplied and the reaction was carried out at a reaction pressure of 13 kg/c+n 2G. The results of these reactions are shown in Table 2.

The complexes prepared by the methods of Examples 1 to 6 have high catalytic efficiency;
It is clear that benzene by-product is also small.

Example 11 η'-1,5-cyclooctadiene-η5- as a catalyst
Methoxyluponylcyclopentagenyl cobalt (catalyst 1) 26 mg (0.09 mm.

I), phenylacetylene 10g, acetonitrile 20g
1 g and 50 ml of toluene at a temperature of 130°C.
The reaction was allowed to proceed for 20 minutes.

As a result of analyzing the product by liquid chromatography, the amount of 2-methyldiphenylpyridine produced was 2.

At 24 g, the catalyst efficiency was 1'O O mat/Co g atom.

Example 12 Using 76 mg of the same catalyst as in Example 11, acetylene and benzonitrile were reacted. The amount of preparation is benzonitrile 2
0g, toluene 60ml, reaction temperature 130°C,
The reaction pressure was 10 kg/am 2G and the reaction was carried out for 60 minutes.

Results of analyzing the product using gas chromatography.

20.2 g of 2-phenylpyridine was obtained, and the catalyst efficiency was 458 mol/Co g atom.

Example 13 Using hydrogen cyanide instead of benzoni I.
The same procedure as in Example 12 was carried out except that 18 kg7 am'G was used for the reaction. As a result, pyridine was obtained and the catalyst efficiency was 4 6 mol/Co g atom.

Catalysts (V) to (■) of Comparative Examples 1 to 3 were used instead of catalyst (1).
When a similar reaction was carried out using , only a trace of pyridine was observed.

Example 14 Argon thermometer η4-cyclooctatetraene-η5- as a catalyst was placed in a 100 ml pressure glass reactor.
Methoxyluponylcyclopendienyl cobalt 30
ing (0, 107 mmol), acetonitrile 2
．． After charging 5 g and 60 ml of toluene, ethyl acetylene was blown in little by little while the reactor was deeply cooled to condense about 10 ml of liquid ethyl acetylene. The reactor was capped and heated at 120°C for 4 hours.

After cooling, the reaction solution was analyzed using a gas chromatograph.
0.72 g of 2-methyldiethylpyridine was obtained, and the catalyst efficiency was 4 4 mol/Co g atom.

Example 15 η4-butadiene-η5-methoxylponylcyclopentadienyl cobal l-2 5mg. (
The reaction was carried out in exactly the same manner as in Example 14, except that 0.104 m river 01 was used.

As a result, 0.47 g of 2-methyldiethylpyridine was obtained, and the catalyst efficiency was 30 mol/Co g atom.

Applicant RIKEN Denki Kagaku Kogyo Co., Ltd. Agent Yutaka 1) Zen M1 Procedural amendment December 7, 1981 Kazuo Wakasugi, Commissioner of the Patent Office 1, Case indication patent application No. 1981-193951 2, Invention Name of η5-methogine carbonyl cyclopentadienyl cobalt complex 6, Person making the amendment Relationship to the case Patent applicant 2-1 Hirosawa, Wako City, Saitama Prefecture (679) RIKEN Representative Ryuko Kanjima Tokyo Chiyo 14
” 1-4-1 Yurakucho, Tokyo (329) 'Fh: Kiikagaku Kogyo Co., Ltd. Representative Akira Shinohara 4, Agent Room 204, Sanshin Building, 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Telephone: 50'1-21385 , 4 Oka 6 of "Detailed Description of the Invention" of Object of Amendment Iv111Vl),
Contents of the amendment The detailed description of the invention is corrected as follows.

1) Page 9, line 9 of the specification r (VJI) J by r (Vll). 2) Page 17, line 11, ``Etheracetylene'' All 1 ethyl acetylene''.

3) Page 23, line 16 rC77, 84, H5, 12J to rC79, 84°H5
, 42J Q4) Page 17, line 11, "η4-norbornadiene" is corrected to [η4-1,5-cyclooctadiene].

5) No. 29 Sada Table 1 ” Correct to.

6) Table 1 on page 29 The catalyst efficiency of Example 9 "87" is corrected to r140J.

Procedure Amendment Book 1981 IQJ 195th Director General of the Patent Office Kazuo Wakasugi 1, Special indication of J¥ sex! fi No. 57-193951 2, Name of the invention η5-methoxyluponylcyclopentaenyl cobalt complex 3, Person making the amendment Relationship to the case Φ Patent applicant 2-1 Hirosawa, Wako City, Saitama Prefecture (θ78) Physical and Chemical Research Representative: Ryuko Miyajima, 1-4-1 Yurakucho, Chiyoda-ku, Tokyo (3211) Denki Kagaku Kogyo Co., Ltd. Representative: Akira Shinohara 4, Agent: Sanshin Building 204, 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Room No. 501-2138 Toyoguchi 1 Naigai Patent Office (5941) Patent Attorney Yutaka 1) Yoshio 5
, "Claims J" and "Detailed Description of the Invention" column 6 of the specification to be amended, Contents of the amendment 6-1 The claims are corrected as shown in the attached sheet.

6-2 The detailed description of the invention is corrected as follows.

l) "Substituted pyridine" in page 17, line 11 and line 11, line 16 of the specification is corrected to "pyridine and its homologues."

Claims l) Formula (1) % Formula % () [In formula (1), R1 is a carbon i having 2 to 4 double bonds
a4 to 12 unsubstituted polyenes or substituted polyenes having 1 to 4 substituents, and the cobalt atom is a coordinating bond with the diene moiety in the polyene (the substituent has 1 to 4 carbon atoms). 4 alkyl groups, phecol groups, or cyanomethylene groups). However, R8 excludes polyenes consisting only of aromatic rings. ] Or formula (II) 1 In formula (II), R2 is a substituted or unsubstituted meclocyclic cyclopentadiene residue (the substituent has 1 to 1 carbon atoms)
4 ([alkyl group or phenyl group, number of substituents is 1
~4 pieces). ] Or Formula (Ill) 1 In Formula (1), R2 is the same as R2 in Formula (II).

η゛-methoxycarbonylcyclopentadienylcobaltboriene complex represented by ~12 unsubstituted polyenes or substituted polyenes having 1 to 4 substituents (the substituents are alkyl groups having 1 to 4 carbon atoms, phecol groups, or cyanomethylene groups). However, W3 is composed only of aromatic rings. Excluding polyenes consisting of

or 11) substituted or unsubstituted acetylene (the substituent has 1 carbon number)
~4 alkylno^ or phenyl groups, the number of substituents is 1 to 2) Formula (1) [In (1), R is a double bond] An unsubstituted polyene having 4 to 12 carbon atoms or a substituted polyene having 1 to 4 ri substituents, in which the cobalt atom has a coordinate bond with the diene moiety in the polyene. (The substituent is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or cyanomethylene 18). However, R1 excludes polyenes consisting only of aromatic rings. ] Or formula (II) P(C6Hs)3 1 In formula (II), R2 is a substituted or unsubstituted meclocyclic cyclopentadiene residue (the substituent has 1 to 4 carbon atoms)
alkyl group or phenyl group, the number of substituents is 1 to 4
). ” or formula (Ill) [In formula (m), R2 is the same as R2 in formula (11).

] A method for producing a η5-methoxyluponylcyclopentadienylcopaltoboriene rust body.

3) JI by cyclization reaction of alkynes and nitriles
In reactions producing substituted or substituted pyridines.

Formula (1) 1 Formula (1) rJJ. u, is an unsubstituted polyene having 2 to 4 double bonds and 4 to 12 carbon atoms or a substituted polyene having 1 to 4 substituents, and the copal I atom is the diene moiety in the polyene. (
The substituent is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a cyanomethylene group. However, R1 excludes polyenes consisting only of aromatic rings. ] Or formula (1■) P (C6R5) 3 [In formula (If), R2 is a substituted or unsubstituted meclocyclic cyclopentadiene residue (the substituent has 1 to 4 carbon atoms)
alkyl groups or phenyl groups, substituted) 1 (the number of is 1
~4 pieces). ] Or formula (III) [Formula (1) width, R2 is the same as R2 of formula (l[).

] A manufacturing method characterized in that a η゛)-methoxylponylcyclopentadienylcopaltoboriene complex represented by the following formula is present as a catalyst.

4) Formula (1) [In formula (1), R1 is an unsubstituted polyene having 4 to 12 carbon atoms having 2 to 4 type 2 packing or a substituted polyene having 1 to 44V4 substituents, The cobalt atom is a cobalt atom that is coordinately bonded to the diene moiety in the polyene (the substituent is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a cyanomethylene group). However, R excludes polyenes consisting only of aromatic rings. J or formula (1 [) % formula %) [In formula (11), R2 is a substituted or unsubstituted meclocyclic cyclopentadiene residue, ((substituent has 1 carbon number)
~4 alkyl groups or phenyl groups, number of substituents is 1
~4 pieces). ] Or formula (11) [In formula (II), R2 is the same as R2 of formula (11). ] Alkynes consisting of η′・-methoxycarbonylcyclopentadienyl cobalt polyene complex and 2I
・A reaction catalyst that produces unsubstituted or substituted pyridine from compounds through a cyclization reaction.

1110-

Claims (1)

[Scope of Claims] 1) Formula (1) [In formula (1), R represents an unsubstituted polyene having 4 to 12 carbon atoms having 2 to 4 double bonds or 1 to 4 substituents; The cobalt atom is a substituted polyene having a cobalt atom that is coordinately bonded to the diene moiety in the polyene (the substituent is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a cyanomethylene group). However, R excludes polyenes consisting only of aromatic rings. ] Or formula (II) [In formula (11), R2 is a substituted or unsubstituted meclocyclic cyclopentadiene residue (the substituent is a carbon @ 1 to 4
alkyl group or phenyl group, the number of substituents is 1 to 4
). ] Or formula (1■) [In formula (III), R2 is the same as R2 in formula (II). ] η5-Methoxyluponylcyclopentadienylcobaltboriene complex. 2) Methoxycarbonylcyclopentagenyl sodium and tristriphenylphosphine cobalt monohalogenide are reacted, and 1) an unsubstituted polyene having 4 to 12 carbon atoms having 2 to 4 double bonds or 1 to 4
Substituted polyene having 3 substituents (the substituents have 1 to 1 carbon atoms)
4 Al-J-Runos! , phenyl di, (or cyanomethylene group). However, R1 excludes polyenes consisting only of aromatic rings. or 11) substituted or unsubstituted acetylene (the substituent has 1 carbon number)
~4 alkyl groups or phenyl groups, number of substituents is 1
Formula (I), characterized in that it is reacted with one or more members from the group consisting of Substituted polyenes or substituted polyenes having 1 to 4 substituents, cobalt-based polyenes are those in which the diene moiety in the polyene has a coordination bond (the substituent is an alkyl Ay having 1 to 4 carbon atoms). 3, phenyl group, or cyanomethylene, 4k). However, R excludes polyenes consisting only of aromatic rings. ] Or formula (II) [In formula (II), R2 is a substituted or unsubstituted meta-9 cyclocyclopentadiene residue (the substituent has 1 to 1 carbon atoms)
4 alkyl groups or phenyl groups, number of substituents is 1 to
4 pieces). ] Or formula (Ill) [In formula (III), R2 is the same as R2 in formula (II). ] A method for producing a η5-methoxyluponylcyclopenkdienylcopaltoboriene complex. 3) In the reaction of producing unsubstituted or substituted pyridine from alkynes and nitriles by cyclization reaction, formula (I) [formula (1) width, R1 has 4 carbon atoms having 2 to 4 double bonds; ~12 unsubstituted polyenes or 1 to 4 1u substituents h! In a mono-substituted polyene, the cobalt atom is a coordinating bond with the diene moiety in the polyene (the substituent is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a cyanomethylene group). However, R1 excludes polyenes consisting only of aromatic rings. ] Or formula (II) [In formula (II), R2 is a substituted or unsubstituted meclocyclic cyclopentadiene residue (the substituent has 1 to 1 carbon atoms)
4 alkyl groups or phenyl groups, number of substituents is 1 to
4 pieces). ] Alternatively, a η5-methoxylponylcyclopentadienylcobaltboriene complex represented by formula (III) [in formula (I''), R2 is the same as R2 in formula (II)] is present as a catalyst. A production method characterized by The cobalt atom is a cobalt atom that has a coordinate bond with the lysene moiety in the polyene (the substituent is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a cyanomethylene group).However, R1 is an aromatic Excluding polyenes consisting only of group rings.] Or formula (11) In formula (n), R2 is a substituted or unsubstituted meclocyclic cyclopentadiene residue (the substituent is an alkyl group having 1 to 4 carbon atoms or phenyl The number of groups and substituents is 1 to 4)] or η5-methoxycarbonylcyclo represented by formula (Ill) c in formula (III), R2 is the same as R2 in formula (II) A reaction catalyst that produces unsubstituted or substituted pyridine through a cyclization reaction from alkynes and nitriles consisting of a pentagenyl cobalt polyene complex.